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Separation of oily sludge and glycerol from biodiesel processing waste by

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 Songklanakarin J. Sci. Technol.
33 (6), 699-703, Nov. - Dec. 2011
http://www.sjst.psu.ac.th

Original Article

Separation of oily sludge and glycerol from biodiesel processing waste

by coagulation
Qiao-guang Xie1, Wirach Taweepreda 2, Charongpun Musikavong1* and Chaisri Suksaroj1*
1
Department of Civil Engineering, Faculty of Engineering,

2
Department of Materials Science and Technology, Faculty of Science,
Prince of Songkla University, Hat Yai, Songkhla, 90112 Thailand.

Received 20 August 2010; Accepted 18 October 2011

Abstract

Raw waste glycerol is a by-product of biodiesel production from transesterification, which is high in salt, and has a high
pH value (more than 9.6). The purpose of this research is to reduce the water pollution from waste glycerol by using a
coagulation process and discussing the possibility of waste glycerol reuse. The commercial coagulant (2% by weight), which
was composed by cationic polyamine (PA) 6% and poly-aluminium chloride (PACl) 94% (w/w), was used as coagulant to
treat waste glycerol. The results showed that after acidification and coagulation process, most of the chemical oxygen demand
(COD), biochemical oxygen demand (BOD5), total suspended solids (TSS), and oily sludge (such as fatty acid, methyl ester,
methanol and soap) in raw waste glycerol were removed, except glycerol. The removal efficiencies of COD, BOD5, TSS, soap
and methanol were 96.2%, 93.3%, 98.1%, 100%, and 85.8%, respectively, but the removal efficiency of glycerol was only
65.4%. There was still a certain amount of glycerol (about 147.5g/L) in the solution, which is separated from oily sludge.

Keywords: coagulation, glycerol recovering, oily sludge, water pollution, waste glycerol

1. Introduction Raw waste glycerol contains a variety of harmful

With global warming and the price of fossil fuel rising,
biodiesel is becoming favored as a kind of carbon neutral fuel
(Topaiboul and Chollacoop, 2010). During the biodiesel pro-
duction process by transesterification, oils/fats (triglycerides)
are mixed with methyl alcohol and alkaline catalysts to
produce esters of free fatty acid, with glycerol as a primary by-
product. In general, production of 100 kg of biodiesel yields
approximately 10 kg of raw waste glycerol, which is impure
and of low economic value (Dasari et al., 2005; Chi et al.,
2007).
* Corresponding author.
Email address: mcharongpun@eng.psu.ac.th,
schaisri@eng.psu.ac.th
compounds, such as 12-16% alkalis especially in the form of
alkali soap and hydroxides, and 8-12% methanol, which may
cause water pollution and environmental problems. More-
over, the cost for disposal of raw waste glycerol is quite ex-
pensive (Yazdani and Gonzalez, 2007; Gervásio Paulo da Silva
et al., 2008). In order to reduce the cost for disposal of raw
waste glycerol, it has been suggested to use some methods to
convert waste glycerol into some valuable products. One
application that has been evaluated is the conversion of
crude glycerol into propylene glycol and acetone (Chiu et al.,
2006). Another application being investigated is the fermenta-
tion of glycerol to 1,3-propanediol, which is an intermediate
compound for the synthesis of polymers used in cosmetics,
foods, lubricants, and medicines (Zheng et al., 2008).
Coagulation is a process by which small particles are
separated from a solution in a reasonable amount of time
using simple or pre-hydrolyzed metal salt, such as alum and
700 Q.-G. Xie et al. / Songklanakarin J. Sci. Technol. 33 (6), 699-703, 2011
PACl, polyelectrolyte, or long chain polymers like PA as the
primary coagulation. This process is not only simple and eco-
nomic, but can also effectively reduce levels of COD, BOD5,
TSS color and organic compounds (Yue et al., 2008). In addi-
tion, the coagulation process can remove organic compounds
effectively but not good for glycerol removal (Wang et al.,
1996).
In this study, the raw waste glycerol was pretreated
by acidification with hydrochloric acid (HCl). After pretreat-
ment, the waste glycerol was taken to be treated by PA blend
with PACl in the coagulation process. The effect of acidifica-
tion process and the optimum conditions of coagulation
process were examined.
2. Material and Methods
2.1 Material
Raw waste glycerol samples were collected from the
waste glycerol tank in the Specialized R&D Center for Alter-
native Energy from Palm Oil and Oil Crop, Thailand, in
October 2009. This facility uses alkali-catalyzed transesteri-
fication to produce biodiesel from waste cooking oil and palm
oil. The characteristics of raw waste glycerol samples were
analyzed to measure pH, COD, BOD5, TSS, fatty acids, and
methyl ester in accordance with the standard method (Eaton
and Franson, 2005). The other parameters were analyzed with
different methods; glycerol (ASTM D7637, 2010), soap
(AOCS, 1996), and methanol (ASTM D7059, 2009).
2.2 Acidification pretreatment
The pH of raw waste glycerol was adjusted from 9 to
3 with 0.8 M of HCl. The effect of acidification on raw waste
glycerol in this pH range was studied to indentify the appro-
priate pH value for acidification process in order to separate
soap and oil. An appropriate pH range for acidification was
selected, which provided the concentration of COD, BOD5,
TSS, and soap. Mass fraction of fatty acid and methyl ester
were analyzed with gas chromatography. The treated waste
glycerol with appropriate pH from acidification pretreatment
was taken to the coagulation process.
2.3 Coagulation process
2.3.1 Jar-tests
The jar test apparatus was a Phipps & Bird Inc., Rich-
mond, Virginia, USA apparatus with six stirrers. In the coagu-
lation experiment process, 400 mL of pretreated solution were
prepared and adjusted their pH values by HCl and NaOH. The
pH values of samples were adjusted to different values, the
optimum concentration of commercial coagulant was mixed
with samples to measure the optimum pH value of samples.
2.3.2 Concentration on coagulation
PACl is normally used at pH values between 7 and 9
due to the pH optimize value (Tzoupanos et al., 2008). Thus,
the pH value of the pretreated solution was adjusted to 7
after acidification pretreatment. The concentration of the
commercial coagulant was varied from 2 g/L to 6 g/L. The
commercial coagulant and waste glycerol was mixed by a jar
test apparatus at 100 rpm for a period of 2 min and then at 35
rpm for 15 min (Meyssami and Kasaeian, 2005). The removal
efficiencies of COD, BOD5, and TSS in coagulated water after
coagulation were measured. The optimum concentration of
the commercial coagulant in total solution was identified by
comparing the removal efficiency.
2.3.3 pH value on coagulation
After pretreatment, the pH value of the pretreated
solution was adjusted to pH values from 9 to 3. The optimum
concentration of the commercial coagulant measured in the
last step was put into different pH values of waste glycerol.
After mixing the commercial coagulant and solution by jar
test apparatus at 100 rpm for a period of 2 min and then at 35
rpm for 15 min (Meyssami and Kasaeian, 2005), the COD,
BOD5, TSS, and organic matters of the samples from waste-
water were measured. The optimum pH value was identified
by comparing the removal efficiencies of COD, BOD5, TSS,
and organic matters.
3. Results and Discussion
3.1 General characteristics of raw waste glycerol
As it is evident from Table 1, waste glycerol has a
high pH value and consists of high concentrations of COD,
BOD5, TSS, and organic matters. The ratio of BOD5:COD had
a value of 0.53, which was difficult for biological treatment
processes. From other values of organic compounds, the raw
waste glycerol can be used as a carbon source or compost.
However, the impurities include methanol and soap and the
Table 1. Selected characterizations of raw waste glycerol.
Characterizations Unit Concentration
pH 9.7-10.4
COD ×106mg/L 1.7-1.9
BOD5 ×106mg/L 0.9-1.2
TSS ×105mg/L 21.3-38.7
Total glycerol g/L 413-477
Soap ×105ppm 2.1-2.7
Methanol g/L 112-203
Water % by weight 9.3-11.9
 Q.-G. Xie et al. / Songklanakarin J. Sci. Technol. 33 (6), 699-703, 2011 701

high pH value would affect the anaerobic or coagulation fractions of fatty acid and methyl ester were 78.8%, 85.9%,
process and utilization of raw waste glycerol. In addition, as and 89.8%, respectively. The oil layer solution can be re-
waste glycerol contains 9.3-11.9% water it cannot be used as covered and reused as a raw material in biodiesel production
a fuel (Peereboom et al., 2007). It could be concluded that
the pH value of raw waste glycerol needs to be reduced, and
soap also need to be removed from the raw waste glycerol
before the coagulation process.

3.2 Effect of acidification process on waste glycerol

3.2.1 Effect of pH on COD, BOD5, and TSS removal

When pH values were in a range of 3 to 7, the soap

were converted into free fatty acids and salt, the waste
glycerol separated into two layers. The oil layer was mainly
free fatty acid and methyl ester; the liquid layer was mainly
glycerol, water and methanol. Samples were taken from the
liquid layer solution to measure COD, BOD5 and TSS. When
pH values were 8 and 9, the samples were taken from waste
glycerol solution. Figure 1. COD, BOD5 and TSS in different pH values.
The concentrations of residual COD, BOD5, and TSS
are shown in Figure 1. The COD and BOD5 of waste glycerol
decreased with the reduction of pH from 9 to 5. The TSS
rapidly increased from pH 9 to pH 8, because when pH value
was 8 a water-in-oil emulsion with a positive charge absorbed
on the interface of the soap and solid particles (Kemmer,
1979). As the pH value was reduced, the neutralization charge
and emulsion were broken, the TSS rapidly reduced from
pH 8 to 7. And then TSS slowly reduced from pH 7 to 5.
In addition, when the pH values were between 3 and 5, the
values of COD, BOD5, and TSS were stable.

3.2.2 Effect of pH on soap removal

Samples were taken from both layers of solution to

measure the concentration of soap. When the pH values
were between 5 and 3, the oil layer solutions were used to Figure 2. Variation of soap concentrations in different layers of
measure the concentration of free fatty acid, methyl ester, waste glycerol.
and impurities. The concentrations of soap in two layers and
total solution, and the mass fraction of fatty acid in the oil
layer solution are shown in Figure 2 and 3. When the pH
value was reduced, the concentration of soap in the two
layers and total solution also decreased, but the mass
fractions of free fatty acid and methyl ester increased. This
indicates that the soluble soap was converted into salt and
insoluble free fatty acid, the chemical equation as follow:

KC17H35COO + HCl  C17H35COOH + KCl (1)

The soap in waste glycerol is potassium soap, since

the potassium hydroxide is usually used as an alkali catalyst
during the biodiesel production process (Gerpen, 2005). In
addition, most of the soap was in the oil layer as shown in
Figure 2. This shows that most of the soap with negative
charge was absorbed by water-in-oil emulsion. Figure 3 Figure 3. Variation of compositions for mass fractions in different
shows that when the pH values were 5 to 3, the total mass pH values (in oil layer solution).
702 Q.-G. Xie et al. / Songklanakarin J. Sci. Technol. 33 (6), 699-703, 2011
processes (Prateepchaikul et al., 2007). It could be concluded
that as a pretreatment the pH values should be adjusted to
5 and the oil layer solution should be removed from waste
glycerol. The acidification process can reduce the COD,
BOD5, TSS, and soap in raw waste glycerol effectively.
3.3 Determination of optimum coagulation conditions
3.3.1 Effect of the commercial coagulant concentration on
parameters removal
The removal efficiencies of TSS, COD, and BOD5 in
different concentrations of commercial coagulant are shown
in Figure 4. When the concentration of the commercial coagu-
lant was 5 g/L, the removal efficiencies of TSS, COD and
BOD5 were maximum value, 92.3% ± 2.2%, 75.5% ± 4.4%, and
87.9% ± 3.0% respectively. After this concentration, the
removal efficiency of COD decreased, and the removal effi-
ciencies of BOD5, and TSS changed slightly. This can be
explained by the influence of excessive PACl on the coagula-
tion (Bogoeva-gaceva, 2010). The optimum concentration of
a commercial coagulant was 5 g/L, which was selected to
carry out the following experiment.
3.3.2 Effect of pH on coagulation
The results of removal efficiencies in different pH
values of waste glycerol are shown in Table 2. The PA blended
with PACl coagulant cannot coagulate waste glycerol in low
pH values. This is because PACl form positive charge alumi-
num species that adsorb negatively charged natural particles,
but when pH values were 3, 4, and 5, the charges of the
particles and soap were positive that cannot adsorb on the
interface of the coagulant. The PA blended with PACl coagu-
lant cannot charge, neutralize, and bridge with particles
between pH 3 and 5 (Avci et al., 2002).
When the pH value of waste glycerol was 7, the
removal efficiencies of TSS, COD, BOD5 reached the maxi-
mum value, and the efficiency of TSS, COD, BOD5, methanol
and glycerol were 98.1% ± 1.5%, 96.2% ± 0.7%, 93.3% ±
1.2%, 85.8% ± 2.9, and 65.4% ± 2.0% respectively. Moreover,
when the pH value is 7, the soap and other impurities were
removed by the coagulation process. The organic and in-
organic matters are removed effectively, except glycerol. The
residual glycerol can be recovered by distillation (Gerpen,
Table 2. Removal efficiencies of parameters in different pH values
(concentration of polymer is 5 g/L)
pH values TSS(%) COD(%)
6 97.3±2.0 64.9±3.4
7 98.1±1.5 96.2±0.7
8 98.9±0.6 82.7±1.6
9 96.1±1.1 95.9±0.9
2005), since the solution separated from coagulation mainly
contains water and glycerol, or can be recovered by cyclo-
dextrin (CD) inclusion complexation from the solution (Song
et al., 2009).
In addition, when the pH value was 7 and the concen-
tration of the commercial coagulant was 5 g/L, the concen-
trations of TSS, COD, BOD5, methanol and glycerol in the
wastewater separated from the coagulation were 118mg/L,
23,311mg/L, 22,416mg/L, 16.5g/L, and 147.5g/L, respectively.
The ratio of BOD5:COD had a value of 0.96, which is higher
than the ratio in the raw waste glycerol (0.53).The free fatty
acid, methyl ester, and soap can reduce the BOD5:COD ratio,
but the coagulation process can remove this oily sludge.
Therefore, the coagulation process can improve the bio-
degradability of waste glycerol.
It can be concluded that the optimum conditions of
the PA blend with PACl coagulating waste glycerol were as
follows: (1) the optimum concentration is 5 g/L; (2) the opti-
mum pH value of waste glycerol for coagulation process is
7; (3) in the conditions of this research, the TSS, COD, BOD5
and methanol were removed effectively. In addition, the oil
and soap, which were toxic matters for microorganisms, were
removed in the coagulation process. Thus, wastewater that
was separated from coagulation was easily treated by bio-
degradation.
Figure 4. COD, BOD5 and TSS in different concentrations of poly-
mer (pH values of solution is 7).
BOD5(%) Glycerol(%) Methanol(%)
65.7±4.2 78.6±2.9 92.1±3.9
93.3±1.2 65.4±2.0 85.8±2.9
84.0±2.9 66.9±1.2 83.4±2.8
90.2±1.6 76.3±2.1 39.5±4.0
 Q.-G. Xie et al. / Songklanakarin J. Sci. Technol. 33 (6), 699-703, 2011
4. Conclusion
On the basis of operation from a laboratory scale
model of PA and PACl coagulation treatment of raw waste
glycerol, the following conclusions can be stated: (1) raw
waste glycerol needs to be pretreated by 0.8M HCl to adjust
the pH value and remove parts of the soap, fatty acid, and
methyl ester, (2) in optimum conditions, the removal efficien-
cies of COD, BOD5, TSS, and organic compounds were
considerable. However, there was still a certain amount of
residual glycerol (147.5g/L) in the solution separated from
coagulation, and (3) the oily sludge produced by the coagu-
lation process of waste glycerol and the commercial coagu-
lant, contains abundant organic matters, which may be used
as an energy resource, carbon source or compost. Addition-
ally, these methods can be used as a pretreatment for the free
fatty acid, methyl ester, and glycerol recovered from waste
glycerol, which can be purified and sold, and by this bring
economic benefits for biodiesel facilities in the future.
Acknowledgements
The authors would like to show their appreciation to
the Faculty of Engineering, (contract reference number ENG-
53-2-7-02-0002-S-1) and the Graduate School, both at the
Prince of Songkla University, Thailand, for financial support.
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